4 The BTX Chain:

Benzene,
Toluene, Xylene

4.1 Overview of the BTX Chain Benzene ranks fifteenth on the list of top fifty
chemicals produced in the United States, with
Benzene, Toluene, and Xylene Are Co- about 15 billion pounds produced in 1997. Most
Products of the benzene produced is used in the
manufacture of ethylbenzene, which is used
Benzene, toluene, and xylene are all aromatic solely to produce styrene and subsequently
compounds1 important to the production of
polymers, other chemicals, and numerous
consumer products (solvents, paints, polishes, Production of Benzene, Toluene, and
pharmaceuticals) (see Figure 4-1). These three Xylene and Their Derivatives (1997)
aromatics are often co-produced by catalytic Benzene (14.9 billion lbs)
reforming of naphtha, although other methods are Ethylbenzene (13.9 billion lbs)
also employed in their manufacture. Toluene, for Styrene (11.4 billion lbs)
Polystyrene (6.4 billion lbs)
example, can be hydroalkylated to form benzene. Cumene (5.8 billion lbs)
Phenol (4.4 billion lbs)
Acetone (2.9 billion lbs)
Cyclohexane (2.2 billion lbs)
Caprolactam (1.7 billion lbs)
Nylon (1.2 billion lbs)
1
In the late nineteenth century “aromatic” referred to Toluene (8.3 billion lbs)
compounds that had low hydrogen-to-carbon ratios Toluene-diisocyanate (0.9 billion lbs)
and were fragrant, as most were made from balsams, p-Xylene (7.9 billion lbs)
o-Xylene (1.1 billion lbs)
resins, or essential oils (e.g., bitter almond oil). Today,
Terephthalic Acid (10 billion lbs)
aromatics are characterized as compounds having fully Phthalic Anhydride (1.0 billion lbs)
conjugated (hybridized unsaturated orbital) ring Adipic Acid (2.0 billion lbs)
structures, which may have 6 carbons, or 10 carbons,
or many more carbons, and may also contain Sources: CMA 1998, SPI 1998.
heteroatoms. Ring structures with 6 carbons like
cyclohexane are called naphthenes, and are not
aromatics.

105
 Figure 4-1. The BTX Chain (CMA 1998)
polystyrene, an important polymer. Small
amounts of styrene are also used in the
manufacture of ABS resins (acrylonitrile-
butadiene-styrene). Ethylbenzene ranked
sixteenth on the top fifty list in 1997, with
nearly 14 billion pounds produced. Styrene
followed closely, with about 11.4 billion pounds
produced. Polystyrene is the fourth largest
thermoplastic produced, with over 6 billion
pounds in 1997. Its primary uses include food
packaging, appliances, and thermal insulation.
About 22 percent of the benzene produced is
used to manufacture cumene, which is used
solely to produce phenol and acetone. Phenol is
an intermediate in the production of phenolic
resins, pharmaceuticals, and various plastics.
Benzene, along with xylene and toluene, is also
used as a component of gasoline. Its use for this
purpose is declining, however, as different
regions of the country impose limits on benzene
because of its known carcinogenicity.
106
Toluene ranked twenty-fifth on the list of the top
fifty chemicals in 1997, with 8.3 billion pounds
produced. More than half of the toluene
produced is used to manufacture benzene by
hydroalkylation. Other important uses are the
production of toluene-diisocyanate (TDI), a
monomer for polyurethanes, and the manufacture
of explosives (TNT).
The most widely used isomers of xylene include
ortho-xylene and para-xylene, named for the
relative position of methyl (CH3) groups on the
six-carbon ring. Ortho indicates the groups are
substituted on adjacent carbons; para indicates
the groups are substituted on the first and fourth
carbons. Demand is much greater for p-xylene,
which ranked twenty-sixth on the list of the top
fifty chemicals in 1997 with about 7.9 billion
pounds of production. It is used primarily to
manufacture terephathalic acid, an important
intermediate in the production of polyester fibers
and resins (see Section 2 for more information
on polyester). Production of o-xylene was about
1 billion pounds in 1997, and this compound is
used almost entirely to make phthalic
anhydride, an intermediate in the synthesis of
plasticizers, pharmaceuticals, and other
chemicals (CMA 1998, CHEMX 1999, Orica
1999.
Demand for BTX and Their Derivatives Is
Closely Linked to the Plastics Market
Like most petrochemicals, the demand for
benzene, toluene, and xylenes is strongly
linked with consumer demand for plastics, their
primary end-use. Currently, the demand for
certain plastics is relatively high demand (e.g.,
polyethylene, polypropylene) but is weakening
for others (e.g., polystyrene, polyvinyl chloride).
Over-capacity, lower demand for exports from
Asia, and declining prices and margins will
continue to be near-term problems for the BTX
chemicals as well as for some of their end-
products.
The demand for cumene, which is produced
from benzene, remains strong, however, and is
being driven by steadily increasing consumption
of bisphenol A, an intermediate in
polycarbonate manufacture, and steady growth
in the use of phenolic resins. Markets for both
of these derivatives are linked to a strong
demand in the downstream consuming
industries of transportation and construction.
The strong underlying global demand for
polyester fibers, film, and bottle resins is
keeping the demand for p-xylene strong. Good
margins have stimulated projects to construct
additional capacity for p-xylene production,
which may lead to overcapacity in the future.
The capacity for o-xylene production is in close
agreement with the demand for this product.
Exports to South American markets have been
increasing, and have helped to offset falling
shipments to the Asia Pacific region. In the
future, some expansion is expected in the use of
o-xylene for herbicides, lubricant additives, and
specialty chemicals manufacture (CHEMX
1999, CHEMWK 1999).
4.1.1 BTX Manufacture
The Same Process Can Be Used To
Produce Benzene, Toluene, and Xylenes
Benzene was originally made solely from coal
tar, until new processes began to emerge in the
1950s. The new production methods were based
on the catalytic reforming of naphtha, and by
1980 they had gradually eliminated the use of
coal tar. Toluene and xylenes are also produced
during the production of benzene using the newer
process. The amounts of each aromatic produced
may vary depending on current market demand,
but typically, production of benzene is favored.
Benzene produced from reformate accounts for
about 40 percent of petrochemical-based
benzene. Another 40 percent is produced by
extracting benzene from pyrolysis gas. About 20
percent is produced by catalytic
hydrodealkylation of toluene or other methods.
A typical flow diagram for production of
benzene, toluene, and xylene from naphtha is
shown in Figure 4-2. Naphtha feed enters a
reactor or series of reactors containing platinum
catalysts in a gas atmosphere (typically hydrogen
to suppress coke formation). Coke is usually
removed from the catalyst and the catalyst is
regenerated and recycled to the reactor.
Hydrogen is also recycled.
The reformate is then subjected to further
processing by various methods, depending on the
desired product slate: (1) solvent extraction of
mixed aromatics, (2) the separation of each
aromatic by distillation, or (3) the hydro-
dealkylation of toluene.
Solvent extraction processes use solvents such as
diethylene glycol, tetraethylene glycol, or
sulfolane to extract the aromatic from non-
aromatic compounds. These solvents also have
high boiling points to make later fractionation of
individual products easier. A typical product
slate for deriving aromatics from naphtha
reformate (which is also subjected to solvent
extraction and fractionation) is shown in Table 4-
1. Fractionation is used to separate and recover
the solvent, which is then returned to the process.
107
 Figure 4-2. Possible Configuration for Reforming of Naphtha To Produce
Benzene, Toluene, and Xylene (Chenier 1992, HP 1999, Orica 1999)

Key Energy and Environmental Facts - Naphtha Reforming to Produce BTX

Energy Emissions Effluents Wastes/Byproducts

Net Energy use:
Process Energy: 1,025 Btu/lb
Feedstock: 299 Btu/lb (based on
refinery stock)
Largest source - fugitive Largest source - process Raffinate, coke, spent
emissions (benzene, toluene, water catalyst
xylenes, solvents)

stream also contains ethylbenzene compounds,

Table 4-1. Product Slate: BTX from
and can be routed to a number of process units,
Naphtha Reformate (% Yield)
depending on the desired products. The bottoms
Benzene 8.5 column from the xylene column contains C9 or
Toluene 26.3 higher aromatics and can be blended into
Xylenes 26.1
TOTAL AROMATICS 74.3
distillates or sold.

Additional processes may be used to optimize

yields of benzene or p-xylene. These processes
When distillation is used, as shown in Figure 4-
may combine special units to produce ultra-high-
2, three columns are used to separate benzene
purity p-xylene with toluene dealkylation units,
first, then toluene, and then mixed xylenes. The
which produce benzene from the toluene product
toluene stream can be sold or rerouted to the
toluene trans-alkylation unit. The mixed xylene

108
 Figure 4-3. Toluene Hydrodealkylation to Produce Benzene (HP 1999, Orica 1999)

Key Energy and Environmental Facts - Toluene Hydrodealkylation

Energy Emissions Effluents Wastes/Byproducts

Net Energy use: Largest source - fugitive Largest source - process water Nonaromatic byproducts
emissions (benzene, xylenes,
Process Energy: 1,117 Btu/lb toluene, solvents)
Feedstock )Hc: 23,330 Btu/lb

stream. The mixed xylene and toluene cuts HDA is shown in Figure 4-3. In this process
from naphtha reformate are the typical toluene is combined with a stream of hydrogen
feedstocks to these units.
Table 4-2. Product Yields from Mixed
There are a variety of technologies available for
C8 Aromatic Streams
production of high-purity p-xylenes from mixed
Downstream Processing
C8 isomer streams. Some are based on
simulated countercurrent adsorption, selective Feed (wt %) Products(wt%)
catalytic isomerization, or a combination of
p-Xylene 14.0 71.1
these with fractionation (xylene splitter). The m-Xylene 41.0 –
C8 feed stream may contain up to 40 percent o-Xylene 19.5 19.6
ethylbenzene, which is converted to xylenes or Ethylbenzene 25.5 --
benzene during the process. Typical yields from
such processes are shown in Table 4-2. Toluene Source: HP 1999.
Note: Based on UOP’s Isomar and Parex processes for
hydrodealkylation (HDA) is also used to selective production of p-xylene.
produce benzene, although it is more costly than
the reforming route (depending on the cost and
availability of hydrogen). A flow diagram for

109
and enters a vessel packed with catalyst.
Current catalysts include chromium or
molybdenum oxides, and platinum or platinum
oxides, supported on silica or alumina.
Operating temperatures are relatively high:
900oF–100oF (480oC–590oC), with pressures
ranging from 40 atmospheres–60 atmospheres.
The catalytic reaction can proceed at lower
temperatures and with higher selectivity, but
requires frequent catalyst regeneration under
these conditions. The reaction is very
exothermic (heat releasing), requiring
temperature control, which is accomplished by
injection of quenching hydrogen at appropriate
places during the reaction. The conversion rate
per pass is as high as 90 percent, and it is
common to obtain cumulative conversions of
greater than 95 percent.
The products pass through a separator to remove
hydrogen, which is recycled. Fractionation is
then used to separate other aromatics and non-
aromatics from the benzene product. HDA units
can usually be operated with feeds of differing
aromatic content, and can be used to produce
primarily benzene or a mix of benzene and
xylenes, depending on the desired product slate.
A typical feed containing about 47 percent
toluene and 50 percent C8 aromatics yields
about 76 percent of benzene by weight (Process
Description: Orica 1999, HP 1999).
4.1.2 Ethylbenzene Production
Ethylbenzene Is Produced through
Friedel-Crafts Alkylation
Early methods for producing ethylbenzene from
benzene and ethylene were based on an
electrophilic aromatic substitution reaction
(Friedel-Krafts alkylation), conducted in the
vapor phase using boron trifluoride, phosphoric
acid, or alumina-silica as catalysts. Since 1980,
ethylbenzene has been produced using zeolite
catalysts in a liquid phase operation.
The flow diagram for producing ethylbenzene
using zeolite catalysts is shown in Figure 4-4.
Ethylene and benzene enter a liquid-filled
110
alkylation reactor that contains fixed beds of
zeolite catalyst. The reaction is very exothermic
(heat-producing), and heat is recovered as low-
pressure steam. The process is generally a net
energy producer, with some of the energy used
to supply heat for the distillation of products.
Since nearly all the ethylbenzene produced (99
percent) is used to produce styrene, this process
is usually integrated with styrene production,
which is very energy-intensive.
The product, mostly ethylbenzene and small
amounts of polyethylbenzene, then enters a
transalkylation reactor containing additional
catalyst, which converts the polyethylbenzene to
ethylbenzene. Effluents from both reactors pass
through a benzene column to remove and
recover unreacted benzene. The reaction
requires excess benzene, in ratios of about 1:0.6
benzene to ethylene. The unreacted benzene is
fed to a vent-gas column to remove impurities.
The ethylbenzene-rich bottoms from the
benzene column are sent to an ethylbenzene
column to remove recyclable alkylbenzenes and
other byproducts.
A product with a purity as high as 99.95 to
99.99 percent can be achieved with a benzene
feedstock of only moderate to high purity. The
catalysts are highly selective and their expected
lifetime is two to four years before they need to
be regenerated. Regeneration is performed at an
outside facility (Process Description: ANL
1980, Chenier 1992, HP 1999).
4.1.3 Styrene Manufacture
Nearly All Styrene Is Made from
Ethylbenzene by Dehydrogenation
Most of the styrene produced in the United
States is made by dehydrogenation of
ethylbenzene. Technology is also emerging to
recover styrene from raw pyrolysis gasoline
produced during steam cracking of naphtha, gas
oils, or natural gas liquids. About 25 percent of
worldwide styrene production comes from
propylene oxide production, where it is
produced as a byproduct.
 Figure 4-4. Ethylbenzene Manufacture (HP 1999)
Key Energy and Environmental Facts - Ethylbenzene Manufacture
Energy Emissions
Net Energy use: Largest source - fugitive
emissions (benzene, ethylene,
Process Energy: 1,174 Btu/lb ethylbenzene)
Feedstock )Hc: 19,044 Btu/lb
Yields of styrene by this process are
considerably higher by a ratio of about 2:1 than
by dehydrogenation of ethylbenzene (DOW
1999). Many plants integrate production of
ethylbenzene with styrene to make use of the
energy exported during ethylbenzene
production. A typical configuration is shown in
Figure 4-5. In this process, the ethylbenzene is
catalytically dehydrogenated to styrene in the
presence of steam. The process is conducted at
high temperatures of 1200oF (2100oC) and
greater, and under vacuum.
The ethylbenzene feed and primary steam are
mixed with superheated steam and
dehydrogenated in a multi-stage reactor. One or
two plants in the United States are injecting air
or oxygen between stages to oxidize the
hydrogen produced, reheat process gas, and
lower equilibrium limits for the
dehydrogenation reaction. However, no air or
Effluents Wastes/Byproducts
Largest source - process water Residues, vent gas
oxygen is injected in the majority of styrene
plants based on ethylbenzene dehydrogenation.
Effluents from the reactor are cooled, which
permits recovery of waste heat and condenses
hydrocarbons and steam. Off-gases are
compressed and later utilized as fuel.
Condensed hydrocarbons are sent to a
fractionation train, where high-purity styrene,
unreacted ethylbenzene, and byproducts (minor
amounts of tar, toluene, and benzene) are
separated and recovered. Benzene, toluene, and
unreacted ethylbenzene are recycled; tar
residues are used as fuel. Conversion of
ethylbenzene can be as high as 80–90 percent.
Various metal oxides can be used as catalysts,
including zinc, chromium, iron, or magnesium
oxides coated on activated carbon, alumina, or
111
 Figure 4-5. Styrene Manufacture (ANL 1980, HP 1999)
Key Energy and Environmental Facts - Styrene Manufacture
Energy Emissions
Net Energy use: Largest source - fugitive
emissions (benzene, toluene,
Process Energy: 16,891 Btu/lb styrene, ethylbenzene)
Feedstock )Hc: 20,058 Btu/lb
bauxite. Iron oxide or potassium carbonate are
also sometimes used. Styrene readily
polymerizes to polystyrene, so sulfur or an anti-
oxidant (p-t-butylcatechol) is usually added to
inhibit polymerization (Process Description:
ANL 1980, Chenier 1992, HP 1999).
4.1.4 Polystyrene Manufacture
Polystyrene Is Usually Made by Bulk
Polymerization
Continuous bulk polymerization processes are
among the least costly and least energy-
intensive methods for producing polystyrene
from styrene monomers, and are therefore used
most frequently. Most bulk processes can make
a range of products, including high-impact
polystyrene, styrene acrylonitrile resins, general
purpose (crystal) grade polystyrene, and certain
112
Effluents Wastes/Byproducts
Largest source - process water Tar residues, benzene,
toluene
specialty grades such as high-gloss, high-
strength polystyrene.
Polymerization of styrene can occur very easily
at room temperatures, without a catalyst or an
initiator, but it can take months to accomplish.
If heated to 300oF (149oC), polymerization
occurs within hours. If an initiator is added
along with heat, the reaction can be completed
in less than an hour. Most processes use
initiators at moderate temperatures to ensure
the high molecular weight and strength of the
product and prevent the possibility of a
runaway reaction.
Polymerization can be accomplished in either
batch or continuous processes. Various
configurations are possible for continuous
styrene polymerization, but most have a similar
process flow. In a typical process, styrene
 Figure 4-6. Polystyrene Manufacture (ANL 1980, HP 1999)
Key Energy and Environmental Facts - Polystyrene Manufacture
Energy Emissions
Net Energy use: Largest source - fugitive
emissions (volatile
Process Energy: 2,264 Btu/lb hydrocarbons, styrene)
Feedstock )Hc: 20,058 Btu/lb
is sent to a prepolymerizing reactor where it is
heated (see Figure 4-6). Partial polymerization
occurs to various degrees upon heating,
depending on the specific operating parameters
of the process. The viscous, partially
polymerized solution is then fed to a
continuously stirred reactor, plug-flow reactor,
or tower, along with initiators.
Temperatures in the reactors or towers are
carefully varied from 230oF to 350oF (110oC to
177oC) to achieve the desired polymerization
rates. The desired molecular weight and
molecular weight distribution of the products
can be controlled by adjusting process
conditions and additives.
Effluents Wastes/Byproducts
Largest source - process water Off-grade polymer
After heating to more than 500oF (260oC), the
viscous molten polymer is pumped out of the
tower through small die holes to form strands.
These strands are then cooled and cut into
pieces for bulk storage and shipment. They may
be used in this form or blended later with
additives and extruded again.
Unreacted styrene monomer is flashed into a
vacuum, and then recovered for separation and
recycling. Styrene can also be removed from
the polystyrene product by vacuum rolling, in
which mechanical work raises the temperature
and volatilizes light components, or by screw
devolatilization, a rapid process that minimizes
degradation of the polymer.
113
During batch polymerization, the styrene feed is
sent to a prepolymerization reactor, typically an
autoclave, to increase its molecular weight.
During prepolymerization, small amounts of
lubricant, plasticizer, polymerization regulator,
and anti-oxidant may be added to the feed. The
blended feed is pumped from the
prepolymerization reactor into a batch reactor,
where some styrene vaporizes and is vented
through an overflow drum. The mixture is
heated and an initiator may be added to drive the
polymerization.
After polymerization is complete, the molten
polymer is pumped to a devolatilizer to remove
residual styrene monomer, ethylbenzene, and
polymers of low molecular weight. The molten
polystyrene is heated, extruded through dies,
and immersed in a cold water bath. It is then
pelletized and sent to bulk storage. Conversion
of styrene is usually higher in batch processes.
Although bulk polymerization is the most
commonly used method, polystyrene can also be
produced using suspension polymerization. In
this process, batches of styrene, initiators, and
water (for heat removal) are added to stirred
kettle reactors or jacketed cylinders, achieving a
conversion rate of 90-93 percent. The small
polymer beads that result are centrifuged, dried,
and stored.
Polystyrene foam can be made by the absorption
of a volatile hydrocarbon (e.g., pentane,
propylene, methylene chloride) during
polymerization. Upon heating with steam or
boiling water, the volatilized beads expand to
produce a foam product (Process Description:
ANL 1980, EPA 1991b, HP 1999).
4.1.5 Cumene Manufacture
Cumene Is Made from Propylene and
Benzene Using Friedel-Crafts Alkylation
Cumene is produced by the Friedal-Crafts
alkylation of benzene and propylene over a
catalyst. Catalysts may include solid acid
phosphoric acid, or one of the new generation of
zeolite catalysts. A new process for producing
114
cumene uses catalytic distillation based on
zeolite catalysts, which has undergone
demonstration trials. A large commercial plant
was scheduled for start-up in Taiwan in 1999.2
Most new plants for cumene production use
processes based on the less corrosive zeolite
catalyst.
In a typical alkylation process, refinery- or
chemical-grade liquid propylene and benzene
are introduced to a fixed-bed alkylation reactor,
where the propylene is consumed completely by
the benzene (see Figure 4-7). The effluent from
the alkylation reactor is sent to a column to
remove propane, which enters in small
quantities with the propylene. The bottoms
from this column are sent to a benzene column
where unreacted benzene is distilled and
recycled. Effluent from this column proceeds to
a cumene separation column to recover the
cumene product as an overhead stream.
The byproduct from the cumene column is
diisopropylbenzene (DIPB). The DIPB is
separated from a small quantity of heavy
hydrocarbon byproduct and recycled along with
benzene to a transalkylation reactor, where the
DIPB reacts with benzene to produce additional
cumene. With the reaction of DIPB, nearly
stoichiometric amounts of cumene are produced
(a yield of nearly 100 percent).
The zeolite catalyst is regenerated (life cycles
are two years or more, with total life of six years
or better), and is non-corrosive. Yields of
cumene of up to 99.97 percent by weight and
better are routinely achieved with this process.
Catalysts are highly selective, environmentally
benign, and generally do not produce oligomers
or coke as byproducts. Zeolite-based processes
are also much more cost-effective and provide
better yields than older processes based on solid
acid catalysts.
The process produces liquified petroleum gases
that can be combusted to produce steam, and
2
Formosa Chemicals & Fibre Corporation
 Figure 4-7. Cumene Manufacture (ANL 1980, HP 1999)
Key Energy and Environmental Facts - Cumene Manufacture
Energy Emissions
Net Energy Exporter: Largest source - fugitive
emissions (volatile
Net Export Steam: 392 Btu/lb hydrocarbons)
Feedstock: 19,032 Btu/lb
the process is a net energy exporter. Since
nearly all the cumene produced is used to make
phenol and acetone (these are co-produced by
the same process), the exported steam is often
utilized in a phenol/acetone manufacturing unit
that is located nearby (Process Description:
Chenier 1992, HP 1999).
4.1.6 Phenol/Acetone Manufacture
Phenol and Acetone Are Co-produced
from Cumene by Hydroperoxidation
The formation of phenol and acetone from
cumene hydroperoxide was first discovered by
German chemists Hock and Lang in 1944 and
Effluents Wastes/Byproducts
Largest source - process water Heavy hydrocarbons,
light gases
was commercialized in the United States and
Europe by 1953. It remains the process of
choice for making over 90 percent of acetone
and phenol produced today (Chenier 1992).
In the first stage of the process (see Figure 4-8),
cumene is oxidized with air to form cumene
hydroperoxide. The reaction proceeds at about
230oF (110oC). The hydroperoxide is then
concentrated and decomposed (cleaved) by acid-
catalyzed rearrangement into acetone and
phenol. The catalyst is removed and the
115
 Figure 4-8. Phenol/Acetone Manufacture (Chenier 1992, HP 1999)

Key Energy and Environmental Facts - Phenol/Acetone Manufacture

Energy Emissions Effluents Wastes/Byproducts

Net Energy use: Largest source - fugitive Largest source - caustic and Spent catalyst,
emissions (cumene, phenol, other wastewaters acetophenone, 2-
Process Energy: 7,850 Btu/lb acetone, AMS) phenylpropan-2-ol, and
Feedstock )Hc: 15,112 Btu/lb alpha-methylstyrene

effluent neutralized before being sent to a
fractionator for separation into high purity
products. Byproducts may include
acetophenone, 2-phenylpropan-2-ol, and alpha-
methylstyrene. The alpha-methylstyrene and
acetophenone are sometimes recovered as useful
products, or may be recycled back to the
hydroperoxidation unit.
After initial fractionation, a series of steps may
be required in order to purify the acetone and
the phenol. These may include hydroextractive
distillation, catalytic treatment, and extraction
with caustics. The purity of products is greater
than 99.99 percent by weight (Process
Description: Chenier 1992, HP 1999).

116
 Figure 4-9. Bisphenol A Manufacture (Chenier 1992, HP 1999)
Key Energy and Environmental Facts - Bisphenol A Manufacture
Energy Emissions
Not available Largest source - fugitive
emissions
4.1.7 Bisphenol A Manufacture
Acetone and Phenol Are Used To Make
Bisphenol A, a Building Block for
Polycarbonates, Plastics, and Resins
Acetone and phenol can be used to manufacture
bisphenol A, an important intermediate in the
production of polycarbonates, epoxy resins, and
engineered plastics. A typical process
configuration based on ion-exchange resin
catalyst is shown in Figure 4-9.
Acetone and excess phenol are first reacted in a
catalytic reactor packed with ion exchange resin.
Effluents Wastes/Byproducts
Largest source - wastewater, Tars and heavy ends
produced waters (can be used as fuel)
The water produced in the reaction is separated
and unreacted acetone and a portion of the
phenol are separated from the reaction mixture
by a series of distillations. Acetone is recycled
to the reactor, and the phenol is mixed with
fresh phenol and purified before recycling.
The remaining effluent containing bisphenol A,
phenol, and impurities is crystallized and
washed to remove impurities. The crystals are
then melted and vacuum distilled and subjected
to evaporation to remove residual phenol and
raw bisphenol A. The molten bisphenol A is
solidified to form flakes, pastilles, or prilles
(Process Description: HP 1999).
117
4.1.8 Derivatives of Xylene
Xylenes Are Used To Produce Three
Major Chemicals: Terephthalic Acid,
Dimethyl Terephthalate, and Phthalic
Anhydride
Terephthalic acid (TPA) and dimethyl
terephthalate (DMT), which are primarily used
in the production of polyester fibers, films, and
resins, can both be produced from p-xylene
through different routes. High purity TPA is
produced through oxidation of p-xylene (see
Figure 4-10). In this process, p-xylene and a
solvent (acetic acid) are oxidized with air over
heavy metal catalysts (cobalt, manganese salts
of heavy metal bromides). Terephthalic acid is
formed, with a purity of about 99.6 percent and
a yield of about 90 percent. The crude TPA is
cooled and crystallized, and the acetic acid and
unreacted xylene are evaporated away. The
crystals are then washed with hot water to
remove traces of the catalyst and acetic acid.
Incomplete oxidation usually results in the
formation of small amounts of a byproduct, p-
formylbenzoic acid, which can be removed by
hydrogenation. Recrystallization of the TPA
provides polyester-grade product with a purity
of 99.9 percent.
DMT can be made from crude TPA, or directly
from p-xylene. If DMT is made from TPA, a
series of steps involving oxidation to produce
TPA (as above), esterification, distillation, and

Figure 4-10. Manufacture of Terephthalic Acid and Dimethyl Terephthalate

(Chenier 1992, HP 1999)

Key Energy and Environmental Facts - Terephthalic Acid and

Dimethyl Terephthalate Manufacture
Energy Emissions Effluents Wastes/Byproducts

Net Energy use: Largest source - fugitive Largest source - wastewater Heavy residues,
emissions (xylenes, TPA, aldehydes, methanol, p-
Process Energy: 1,779 Btu/lb DMT) formylbenzoic acid
Feedstock )Hc: 18,843 Btu/lb

118
 Figure 4-11. Manufacture of Phthalic Anhydride (Chenier 1992, HP 1999)
Key Energy and Environmental Facts - Phthalic Anhydride Manufacture
Energy Emissions
Net Energy Exporter: Largest source - fugitive
emissions (xylene)
Steam Export: 1,920 Btu/lb
crystallization are employed (see Figure 4-10).
This processing method can produce both TPA
and DMT if desired. During esterification, the
crude TPA mixture from oxidation is esterified
with methanol and produces a mixture of esters,
usually in the presence of sulfuric acid catalyst.
The ester mixture is distilled (often using a
series of distillation towers) to remove heavy
components and residues. Lighter esters are
recycled. Crude DMT from distillation is sent
to a crystallization section where DMT isomers
and aromatic aldehyde byproducts are removed,
and pure DMT is produced.
DMT can also be made directly from p-xylene
and p-methyl toluate by oxidation over heavy
metal catalysts, followed by esterification, in a
process similar to that just described (Process
Description: HP 1999).
Phthalic anhydride is not a “top-fifty"
chemical, but is an important chemical
intermediate used as a plasticizer and in resins
manufacturing. Phthalic anhydride reacts with
Effluents Wastes/Byproducts
Largest source - wastewater Heavy residues, waste
gases, spent catalyst
some alcohols to form liquids called
plasticizers, which, when mixed with plastics,
give them a greater flexibility without affecting
their strength.
Phthalic anhydride is the primary chemical
made from o-xylene, normally by way of the
von Heyden process (see Figure 4-11). In this
process, the o-xylene is charged with air to a
catalytic multi-tube reactor. An agitated molten
salt removes the heat of reaction to maintain the
proper temperature. The heat of reaction is used
to generate process steam. Effluent from the
reactor is condensed as a solid sublimate, then
melted to produce liquid product. Effluent
gases are vented to the atmosphere after water
scrubbing or incineration. Further purification
is carried out through distillation. The purified
product can be stored in the molten state or
flaked for bulk storage (Process Description:
Chenier 1992, HP 1999).
119
4.1.9 Cyclohexane, Caprolactam, and
Nylons
Both Nylon 6 and Nylon 6,6 Have Their
Origin in Cyclohexane
Cyclohexane, which is derived by the
hydrogenation of benzene over a nickel or
platinum catalyst, is used to manufacture adipic
acid and caprolactam. Adipic acid is the
starting material for Nylon 6,6, one of the first
synthetic polyamides (proteins) ever developed.
Work on nylons originated with researchers at
Du Pont interested in finding a cheap
replacement for silk in stockings. Commercial
production of hexamethyleneadipamide (Nylon
6,6) began in 1940.
The name caprolactam is derived from the
original chemical name for the six-carbon
carboxylic acid, caproic acid. It is manufactured
mostly from cyclohexane or phenol. All
caprolactam is used to make Nylon 6 fibers,
plastic resins, and film. Although not as
predominant as Nylon 6,6, the use of Nylon 6 is
growing rapidly, particularly in Japan.

Figure 4-12. Nylon 6,6 Manufacture (EPA 1990, Chenier 1992, Brown 1996)

Key Energy and Environmental Facts - Nylon 6,6 Manufacture

Energy Emissions Effluents Wastes/Byproducts

Net Energy Use: Largest source - fugitive Largest source - wastewater Fuel/vent gases
emissions (volatilized
Process: 17,166 Btu/lb monomers), oil vapors or mists
Feedstock )Hc: 23,080 Btu/lb

120
 Figure 4-13. Nylon 6 Manufacture (EPA 1990, Chenier 1992, Brown 1996, HP 1999)
Key Energy and Environmental Facts - Nylon 6 Manufacture
Energy Emissions
Net Energy Use: Largest source - fugitive
emissions (volatilized
Process: 11,507 Btu/lb monomers), oil vapors or
Feedstock )Hc: 22,000 Btu/lb mists
Adipic acid is made primarily by nitric acid
oxidation of a cyclohexanone-cyclohexanol
mixture called KA oil (ketone-alcohol) (see Figure
4-12). Air oxidation of cyclohexane is first
accomplished using a cobalt or manganese (II)
naphthenate or acetate catalyst, which produces
the KA oil mixture. The KA oil is then oxidized
with 50 percent nitric acid with ammonium
vanadate and copper present as catalysts. A new
process has also been developed that use nitrous
oxide oxidation of benzene to produce KA oil.
Nylon 6,6 is primarily made by the reaction of
hexamethylene-diamine (HMDA) and adipic acid.
The result is a salt, which is then washed in a
methyl alcohol bath. Polymerization then takes
place in a batch process under heat and pressure.
A typical production process for producing Nylon
6,6, fiber from nylon polymer chips is shown in
Figure 4-12. There are other possible routes for
Effluents Wastes/Byproducts
Largest source - Spent catalyst, ammonium
wastewater sulfate, ammonium
phosphate
production of Nylon 6,6 (e.g., the adipamide
process), although the HMDA method is most
commonly employed.
Caprolactam is made through a series of reactions
in which cyclohexanone is converted into an oxime
with hydroxylamine (see Figure 4-13). The oxime
then undergoes the well-known acid-catalyzed
reaction called the Beckmann rearrangement to
produce caprolactam. Sulfuric or phosphoric acid
compounds may be used as the catalyst, and after
treatment with ammonia, a byproduct is created
that can be sold as a fertilizer.
Nylon 6 is made directly from caprolactam by
heating with a catalytic amount of water in a
continuous polymerization process. It is then spun
into fibers in a fashion similar to that for Nylon 6,6
(see Figure 4-12) (Process Description: ANL 1980,
EPA 1990, Chenier 1992, Brown 1996, HP 1999).
121
4.2 Summary of Inputs/Outputs Styrene
Inputs: Outputs:
The following summarizes the essential inputs and
products, wastes, and byproducts of the chemicals Ethylbenzene Styrene
and chemical products included in the BTX chain. Benzene, Toluene Off Gases
Catalyst Steam
Benzene/Toluene/Xylene (BTX) from Inhibitors/Antioxidants Condensate
Naphtha Process Water Tar Residues
Steam/Fuel Wastewater
Electricity
Inputs: Outputs:
Naphtha or Benzene/Toluene/Xylene Polystyrene
Pyrolysis Hydrogen
Gasoline Water
Ethylbenzene Coke/Energy Export Inputs: Outputs:
Solvent Purge/Flared Gases Styrene Polystyrene Pellets
Inert Gas Process Water Initiators Purge Gases
Catalyst Extraction Raffinate Inhibitors Process Water
Water Spent Catalyst Additives Off-grade Polymer
Steam/Fuel Cooling Water
Electricity Steam/Fuel
Electricity

Benzene from Toluene

Cumene

Inputs: Outputs:
Inputs: Outputs:
Toluene Benzene
Mixed Xylenes Extraction Raffinate Benzene Cumene
Hydrogen Hydrogen Propylene Heavy Hydrocarbons
Catalyst Nonaromatic Byproducts Catalyst Light Gases
Steam/Fuel Process Water Process Water Process Water
Electricity Steam/Fuel
Electricity
Ethylbenzene
Phenol/Acetone
Inputs: Outputs:
Benzene Ethylbenzene Inputs: Outputs:
Ethylene Vent Gas Cumene Phenol
Polyethylbenzene Bottom Residues Air Acetone
Catalyst Water Acid Catalyst "-Methylstyrene (AMS)
Process Water Solvent Wastewater
Fuel/Steam Process Water Spent Catalyst
Electricity Steam/Fuel Organic Byproducts
Electricity

122
Bisphenol A Adipic Acid

Inputs: Outputs: Inputs: Outputs:

Acetone Bisphenol A Flakes, Cyclohexane Adipic Acid
Phenol Pellets, Pastilles, or Prills Air Spent Catalyst
Ion Exchange Reaction-Produced Water Catalyst Vent Gases
Resin Tar Process Water Wastewater
Process Water Heavy Components
Steam/Fuel
Caprolactam
Electricity

Terephthalic Acid, Dimethyl Terephthalate Inputs: Outputs:

Cyclohexane Caprolactam
Inputs: Outputs: Hydrogen Ammonium Sulfate
Acid Catalyst Ammonium Phosphate
p-Xylene Terephthalic Acid Ammonia Wastewater
Acetic Acid Dimethyl Terephthalate Process Water Acid Waste
p-Methyl Toluate Heavy Components Steam/Fuel
Sulfuric Acid Filtrate Electricity
Methanol Isomer Byproducts
Air Process Water
Catalyst Acid Byproducts Nylon 6,6
Process Water
Steam/Fuel
Inputs: Outputs:
Electricity
Adipic Acid Nylon 6,6 Filament or
Phthalic Anhydride HMDA Staple
Process Water Process Water
Steam/Fuel
Inputs: Outputs: Electricity

o-Xylene Phthalic Anhydride

Air Heavy Components Nylon 6
Catalyst High Pressure Steam
Process Water Low Pressure Steam
Inputs: Outputs:
Steam/Fuel Spent Catalyst
Electricity Waste Gases Benzene Cyclohexane
Process Water Hydrogen Fuel Gas
Catalyst Spent Catalyst
Cyclohexane Steam/Fuel
Electricity

Inputs: Outputs:
Benzene Cyclohexane
Hydrogen Fuel Gas
Catalyst Spent Catalyst
Steam/Fuel
Electricity

123
4.3 Energy Requirements
Process Energy Requirements for the BTX
Chain Are Relatively Low
The process and feedstock energy used for the
production of benzene, toluene, xylene, and their
derivatives are shown in Tables 4-3 through 4-15
(ANL 1980, EEA 1983, BIO 1988, Brown 1996,
HP 1997d, HP 1999). Each table provides net
processing energy, which is the energy used to
provide heat and power for the process, in the
form of fuels, electricity, or steam. Feedstock
energy is comprised of two
elements: (1) the net heat of combustion of the
feedstock, and (2) the processing energy required
to manufacture the feedstock. Each table provides
the value of the heat of combustion for the
feedstock chemical(s) at standard conditions
()Hc).
The second component of feedstock energy,
processing energy, is denoted as Feedstock Process
Energy. This is the processing energy required to
manufacture the feedstocks, beginning with the
starting raw crude materials. For example, the
Feedstock Process Energy

Table 4-3. Estimated Energy Use in BTX Manufacture - 1997

Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 62 - 99 81 2.4

Fuel Oil and LPGb 28 - 42 35 1.0

Natural Gas 718 - 1,090 904 226.4

Coal and Coke 93 - 142 117 3.4

Otherc 93 - 142 117 3.4

NET PROCESS ENERGY 994 - 1,515 1,255 36.6

Electricity Losses 129 167 4.9

Energy Export (127) (230) (6.7)

TOTAL PROCESS ENERGY 996 - 1,388 1,192 34.8

d 32,030 32,030 935.3
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 33,026 - 33,418 33,222 970.1

Feedstock Process Energye 390 390 11.4

TOTAL ENERGY EMBODIED IN 33,416 - 33,808 33,612 981.5

BTX MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of naphtha, propane, and butanes (ANL 1980).
e Energy for crude distillation to produce naphtha (EI 1997).
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies, including the IFP CCR Aromizing process and
BP-UOP Cyclar process (HP 1999).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values for benzene, toluene, and xylenes (29.2
billion lbs) (CMA 1998). This number captures the 80 percent of BTX produced from refinery stocks.

124
for propylene oxide includes the energy required
to process ethylbenzene, propylene, ethylene,
benzene, and raw crude.
Total net energy inputs include processing
energy for the final product, plus the heat of
combustion of the feedstocks, minus any steam
or fuel generated by the process. The losses
incurred during the generation and transmission
of electricity (regardless of whether purchased
or produced on-site) are shown as “electricity
losses.” These are added to total net energy to
obtain Total Primary Energy, which is the total
primary energy consumption associated with
production of the individual chemical. Total
Embodied Energy includes the Feedstock
Process Energy, and represents all the energy
consumption that is embodied in the
manufacture of the product beginning with raw
crude.
For every category, energy use for process heat
is distributed according to the various fuel types
used throughout the industry. Fuel distribution
for 1997 was as follows: fuel oil and LPG - 3
percent, natural gas - 77 percent, coal and coke -

Table 4-4. Estimated Energy Use in Benzene Manufacture - 1997

Average Specific f Chemical Industry Energy
Energy Energy (Btu/lb) Use g (1012 Btu)

Electricitya 64 0.2

Energy for Steam/Process Heat f

Fuel Oil and LPGb 32 0.1

Natural Gas 811 2.4

Coal and Coke 105 0.3

c
Other 105 0.3

NET PROCESS ENERGY 1,117 3.4

Electricity Losses 133 0.4

Energy Export 0 0.0

TOTAL PROCESS ENERGY 1,250 3.8

d 23,330 70.0
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 24,580 73.7

Feedstock Process Energye 433 1.3

TOTAL ENERGY EMBODIED IN 25,013 75.0

BENZENE MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of toluene (Perry 1984).
e Energy used to manufacture toluene, including all steps from raw crude feed (see Table 4-3).
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies, including the ABB-Lummus Global process (HP
1999).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values for benzene (3 billion lbs) (CMA 1998).
This number captures the 20 percent of benzene produced directly from toluene.

125
10 percent, and other - 10 percent (CMA 1998).
The “other” category includes any other fuel
source (e.g., byproduct fuel gases).
With few exceptions, little energy is consumed
to provide heat and power during the production
of BTX and derivatives–usually less than
1,500 Btu/lb. The exceptions are for the
production of styrene, phenol and acetone
(which are co-produced), and caprolactam.
Energy requirements for BTX shown in Table
4-3 are based on production from naphtha (a
petroleum fraction) and mixtures of propane and
butane; the feedstock energy data in Table 4-4 is
based on production of benzene directly from
toluene. Total process energy requirements are
similar for both products. Most current
production, however, is from refinery stocks,
which are cheaper and more readily available.
Feedstock energy requirements for BTX
produced from refinery stocks are much higher,
however, due to the highly combustible fuel
content of the feed.

Table 4-5. Estimated Energy Use in Ethylbenzene Manufacture - 1997

Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 42 42 0.6

Energy for Steam/Process Heat f

Fuel Oil and LPGb 38 - 44 41 0.6

Natural Gas 971 - 1127 1,049 14.6

Coal and Coke 126 - 146 136 1.9

Otherc 126 - 146 146 1.9

NET PROCESS ENERGY 1303 - 1505 1,404 19.5

Electricity Losses 87 87 1.2

Energy Export (127) - (333) (230) (3.2)

TOTAL PROCESS ENERGY 1,263 - 1259 1,261 17.5

d 19,044 19,044 264.7
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 20,307 - 20,303 20,305 282.2

Feedstock Process Energye 2,978 2,978 41.4

TOTAL ENERGY EMBODIED IN 23,285 - 23,281 22,283 323.6
ETHYLBENZENE MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of ethylene and benzene (Perry 1984). Stoichiometric ratios: 0.266 lbs
ethylene and 0.739 lbs benzene for every lb of ethylbenzene (HP 1999).
e Energy used to manufacture ethylene and benzene, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies, including CDTECH and Raytheon processes (HP
1999).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (13.9 billion lbs) (CMA 1998).

126
Process and feedstock energy requirements for
ethylbenzene are relatively low, in part because
the process produces export steam (see Table 4-
5). However, as shown in Table 4-6, energy
used in the manufacture of its major derivative,
styrene, is the highest in the BTX chain (about
14,000 Btu/lb). The majority of the energy is
used in the form of steam for dehydrogenation,
preheating, and separation processes. Although
the amount of styrene produced is about one-
fourth that of BTX, the annual energy
consumption associated with its production is
nearly three times that of BTX (110 trillion Btu
compared with 39 trillion Btus for BTX).
Processing energy requirements for polystyrene
are moderate, about 1,400 Btu/lb. A good
portion of the energy is embodied in hot oil that
is used to transfer heat. Small amounts of fuel
and steam are used to supplement the hot oil.
Electricity is used primarily for extruding,
blending, and finishing of the polymer product.

Table 4-6. Estimated Energy Use in Styrene Manufacture - 1997

Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 0 0 0.0

Energy for Steam/Process Heat f

Fuel Oil and LPGb 431 - 582 507 3.3

Natural Gas 11,065 - 14,947 13,006 84.5

Coal and Coke 1,437 - 1,941 1,689 11.0

Otherc 1,437 - 1,,941 1,689 11.0

NET PROCESS ENERGY 14370 - 19,412 16,891 110.0

Electricity Losses 0 0 0.0

Energy Export 0 0 0.0

TOTAL PROCESS ENERGY 14,370 - 19,412 16,891 109.8

d 20,058 - 20,058 20,058 130.4
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 34,428 - 39,470 36,949 240.2

Feedstock Process Energye 4,501 4,501 29.3

TOTAL ENERGY EMBODIED IN 38,929 - 43,971 41,450 269.5

STYRENE MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of ethylbenzene (Perry 1984). Stoichiometric ratios: 1.085 lbs
ethylbenzene for every lb of styrene (Brown 1996).
e Energy used to manufacture ethylbenzene, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies (EEA 1983, Brown 1996).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (6.5 billion lbs) (CMA 1998). Does not
include styrene co-produced with propylene oxide.

127
 Table 4-7. Estimated Energy Use in Polystyrene Manufacture - 1997
Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 84 -195 140 0.9

Energy for Steam/Process Heat f

Fuel Oil and LPGb 40 - 88 64 0.4

Natural Gas 1,015 - 2,256 1,635 10.5

Coal and Coke 132 - 293 212 1.4

Otherc 132 - 293 212 1.4

NET PROCESS ENERGY 1,402 - 3,125 2,264 14.5

Electricity Losses 174 - 405 290 1.9

Energy Export 0 0 0.0

TOTAL PROCESS ENERGY 1,576 - 3,530 2,553 16.3

d 20,058 - 20,058 20,058 128.4
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 21,634 - 23,588 22,611 144.7

Feedstock Process Energye 21,392 21,392 136.9

TOTAL ENERGY EMBODIED IN 43,026 - 44,980 44,003 281.6

POLYSTYRENE MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of styrene (Perry 1984). Stoichiometric ratios: 1.0 lbs styrene for every lb
of polystyrene (Brown 1996).
e Energy used to manufacture styrene, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies (EEA 1983, Brown 1996).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (6.4 billion lbs) (CMA 1998).

The process for manufacturing cumene located in close proximity to phenol/acetone

generates excess steam (about 400 Btu/lb of
product). The annual energy contribution from
this process is about 2.3 trillion Btu beyond the
energy needed for manufacturing cumene (see
Table 4-8). Feedstock requirements for cumene
are based on stoichiometric quantities of
benzene and propylene.
production facilities to make use of the excess
steam. Most of the energy is consumed in
distillation columns during the separation of
acetone and phenol (see Table 4-9). Electricity
is used primarily for compression and
concentration of products.

Production of the major derivatives of cumene,

phenol and acetone, is very energy-intensive,
and the cumene production unit is usually

128
 Table 4-8. Estimated Energy Use in Cumene Manufacture - 1997
Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 5 - 17 11 0.1

Energy for Steam/Process Heat f

Fuel Oil and LPGb 17 - 24 21 0.1

Natural Gas 444 - 610 527 3.1

Coal and Coke 58 - 79 68 0.4

Otherc 58 - 79 68 0.4

NET PROCESS ENERGY 582 - 809 696 4.0

Electricity Losses 10 - 35 23 0.1

Energy Export (982) - (1243) (1,113) (6.5)

TOTAL PROCESS ENERGY (390) - (399) (394) (2.3)

d 19,032 19,032 110.4
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 18,642 - 18,633 18,638 108.1

Feedstock Process Energye 1,643 1,643 9.5

TOTAL ENERGY EMBODIED IN 20,285 - 20,276 20,281 117.6

CUMENE MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of benzene and propylene (Perry 1984). Stoichiometric ratios: 0.651 lbs
benzene and 0.351 lbs propylene for every lb of cumene (HP 1999).
e Energy used to manufacture benzene and propylene including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies, including those licensed by CDTECH, Raytheon
Engineers & Constructors, and UOP (HP 1999).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (5.8 billion lbs) (CMA 1998).

Feedstock requirements for phenol/acetone and purification operations needed to produce a

production are also high. Approximately 1.3
tons of cumene are required for every ton of
phenol/acetone product.
Process energy required for terephthalic acid
(TPA), another important derivative of cumene,
can vary considerably depending on whether it
is made directly from p-xylene and methanol, or
from DMT (dimethyl terephthalate) (see Table
4-10). Electricity requirements can be
significant, reaching nearly 50 percent of total
energy use, primarily because of the filtering
polymer-grade product, i.e., a product of 99.5
percent and greater purity). Feedstock
requirements for TPA are based on production
from p-xylene and methanol.
When electricity losses are excluded, the
processes used for production of phthalic
anhydride are net energy producers. The
estimates published for utilities for these
processes vary from a net energy export of about
958 Btu/lb to over 5,000 Btu/lb, depending on
the feedstock used. Higher

129
 Table 4-9. Estimated Energy Use in Phenol/Acetone Manufacture - 1997
Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 300 484 392 2.9

Energy for Steam/Process Heat f

Fuel Oil and LPGb 172 - 276 224 1.6

Natural Gas 4404 - 7081 5,743 41.9

Coal and Coke 572 - 920 746 5.4

Otherc 572 - 920 746 5.4

NET PROCESS ENERGY 6020 - 9680 7,850 57.3

Electricity Losses 623 - 1005 814 5.9

Energy Export 0 0 0.0

TOTAL PROCESS ENERGY 6643 - 10685 8,664 63.3

d 15,112 15,112 110.3
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 21,755 - 25,797 23,776 173.6

Feedstock Process Energye 2,188 2,188 1.6

TOTAL ENERGY EMBODIED IN 23,943 - 27,985 25,964 175.2

PHENOL/ACETONE MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of cumene (Perry 1984). Stoichiometric ratios: 0.81 lbs cumene for every
lb of phenol/acetone product (HP 1999).
e Energy used to manufacture cumene, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies (EEA 1983, Brown 1996).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (7.3 billion lbs) (CMA 1998).

amounts of electricity are derived from
naphthalene feedstock, and lower amounts from
o-xylene. Electricity requirements are estimated
at about 1400 Btu/lb (ANL 1979, CEH 1999).
Process energy consumed for cyclohexane
manufacture is low, primarily because the
process is relatively uncomplicated and is a
large net exporter of steam. Net process energy
requirements after steam export, and including
electricity losses, are only a little over 600
Btu/lb (see Table 4-11). However, the major
derivatives of cyclohexane are energy-intensive,
and account for a considerable amount of energy
consumed.
Cyclohexane is used to make adipic acid, an
intermediate in the production of Nylon 6,6. As
seen in Table 4-12, the average energy
requirements for adipic acid production are
about 27 times greater per pound than those of
cyclohexane. Annual energy consumption
attributed to adipic acid production is about 35
trillion Btu without losses, and over 42 trillion
Btu when losses are considered.

130
 Table 4-10. Estimated Energy Use in Terephthalic Acid Manufacture - 1997
Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 620 620 6.2

Energy for Steam/Process Heat f

Fuel Oil and LPGb 22 - 48 35 0.4

Natural Gas 557 - 1227 892 8.9

Coal and Coke 72 - 159 116 1.2

Otherc 72 - 159 116 1.2

NET PROCESS ENERGY 1,343 - 2,214 1,779 17.8

Electricity Losses 1,287 1,287 12.9

Energy Export 0 0 0.0

TOTAL PROCESS ENERGY 2,630 - 3,501 3,066 30.7

d 15,369 - 22,316 18,843 188.4
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 17,999 - 25,817 21,908 219.1

Feedstock Process Energye 903 903 9.0

TOTAL ENERGY EMBODIED IN 18,902 - 26,720 22,811 228.1

TEREPHTHALIC ACID MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of p-xylene and methanol (ANL 1980, Perry 1984). Stoichiometric ratios:
0.715 lbs p-xylene and 0.06 lbs methanol for every lb of terephthalic acid (HP 1999).
e Energy used to manufacture p-xylene and methanol, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies, including those licensed by Degussa-Huls AG and
others (EEA 1983, HP 1999).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (10 billion lbs) (CMA 1998).

Another important derivative of cyclohexane is
caprolactam, an intermediate in the production
of Nylon 6. Average process energy
requirements for caprolactam are also relatively
high, about 13,000 Btu/lb when losses are
considered, about 21 times greater than the
process energy required for cyclohexane
manufacture. Annual process energy consumed
for caprolactam manufacture is over 22 trillion
Btu (without considering losses).
Most of the energy consumed for both adipic
acid and caprolactam manufacture is in the form
of fuels combusted to produce steam for process
heat. The thermal efficiencies of steam systems
are variable, and can range from as low as 55
percent to as high as 85 percent, depending on
heat losses from the stack and other areas. This
variability creates a degree of uncertainty in
data on energy consumption. Electricity is used
for compression and pumping, but generally
accounts for less than 10 percent of energy use.

131
 Table 4-11. Estimated Energy Use in Cyclohexane Manufacture - 1997
Average Specific f Energy Chemical Industry Energy
Energy (Btu/lb) Use g (1012 Btu)

Electricitya 150 0.3

Energy for Steam/Process Heat f

Fuel Oil and LPGb 48 0.1

Natural Gas 1,227 2.7

Coal and Coke 159 0.4

Otherc 159 0.4

NET PROCESS ENERGY 1,743 3.8

Electricity Losses 311 0.7

Energy Export (1,416) (3.1)

TOTAL PROCESS ENERGY 638 1.4

d 21,224 46.7
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 21,862 48.1

Feedstock Process Energye 1,680 3.7

TOTAL ENERGY EMBODIED IN 23,542 51.8

CYCLOHEXANE MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of benzene and hydrogen (ANL 1980, Perry 1984). Stoichiometric ratios:
0.93 lbs benzene and 0.075 lbs hydrogen for every lb of cyclohexane (ANL 1980).
e Energy used to manufacture benzene and hydrogen, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies (ANL 1980, Brown 1996).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (2.2 billion lbs) (CMA 1998).

Production of Nylon 6,6 requires large Nylon 6 production is also energy-intensive in

quantities of steam for polymerization as well as
melting of the polymer product (see Table 4-14).
Fuel used for steam production can be as high
as 17,000 Btu/lb. Large quantities of electricity
are also used in the casting, chipping, melting,
spinning, drawing, and winding of finished
nylon fibers (over 3,000 Btu/lb). On average,
electricity accounts for about 20 percent of total
energy consumed. The amount of energy
consumed to produce Nylon 6,6 is
significant–about 14 trillion Btu per year.
terms of steam use. In the continuous
polymerization process, most of the steam is
used for melting, for carrying out the
polymerization reaction, and for concentrating
unreacted caprolactam to recycle it back into the
process. Considerable amounts of steam are
also expended for fiber processing (e.g.,
melting, drying). Electricity is used throughout
the process for pumping, extraction, extruding,
melting, spinning, drawing, and winding, and
accounts for about 13 percent of total energy
use. The greater share of electricity is used in
production of the finished nylon fibers.

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 Table 4-12. Estimated Energy Use in Adipic Acid Manufacture - 1997
Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 1,100 - 2,400 1,750 3.5

Energy for Steam/Process Heat f

Fuel Oil and LPGb 297 - 648 473 1.0

Natural Gas 7,623 - 16,632 12,128 24.3

Coal and Coke 990 - 2,160 1,575 3.2

Otherc 990 - 2,160 1,575 3.2

NET PROCESS ENERGY 11,000 - 24,000 17,500 35.0

Electricity Losses 2,284 - 4,984 3,634 7.3

Energy Export 0 0 0.0

TOTAL PROCESS ENERGY 13,284 - 23,984 21,134 42.3

d 14,414 14,414 28.8
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 27,698 - 43,398 35,548 71.1

Feedstock Process Energye 1,445 1,445 2.9

TOTAL ENERGY EMBODIED IN 29,143 - 44,843 36,993 74.0

ADIPIC ACID MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of cyclohexane (Perry 1984). Stoichiometric ratios: 0.72 lbs cyclohexane
for every lb of adipic acid (ANL 1980).
e Energy used to manufacture cyclohexane, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies (ANL 1980, BIO 1988).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (2.0 billion lbs) (CMA 1998).

133
 Table 4-13. Estimated Energy Use in Caprolactam Manufacture - 1997
Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 624 - 1,239 932 1.6

Energy for Steam/Process Heat f

Fuel Oil and LPGb 249 - 487 368 0.6

Natural Gas 6,380 - 12,489 9,435 16.0

Coal and Coke 829 - 1,622 1,225 2.1

Otherc 829 - 1,622 1,225 2.1

NET PROCESS ENERGY 8,910 - 17,459 13,185 22.4

Electricity Losses 1,296 - 2,573 1,934 3.3

Energy Export 0 0 0.0

TOTAL PROCESS ENERGY 10,206 - 20,032 15,119 25.7

)Hc) d
Heat of Feedstock () 21,027 21,027 35.8

TOTAL PRIMARY ENERGY 31,233 - 41,059 36,146 61.5

Feedstock Process Energye 2,107 2,107 3.6

TOTAL ENERGY EMBODIED IN 35,448 - 43,166 38,253 65.1

CAPROLACTAM MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of cyclohexane (Perry 1984). Stoichiometric ratios: 1.05 lbs cyclohexane
for every lb of caprolactam (ANL 1980).
e Energy used to manufacture cyclohexane, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies, including those licensed by SNIA BPD, Sp.A (BIO
1988, HP 1999).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (1.7 billion lbs) (CMA 1998).

134
 Table 4-12. Estimated Energy Use in Manufacture of Nylon 6,6 - 1997
Specific Energy f Average Specific Chemical Industry
Energy (Btu/lb) Energy (Btu/lb) Energy Use g (1012 Btu)

Electricitya 2,606 - 3,914 3,260 2.6

Energy for Steam/Process Heat f

Fuel Oil and LPGb 334 - 501 417 0.3

Natural Gas 8,560 - 12,855 10,708 8.6

Coal and Coke 1,112 - 1,670 1,391 1.1

Otherc 1,112 - 1,670 1,391 1.1

NET PROCESS ENERGY 13,723 - 20,609 17,166 13.7

Electricity Losses 5,411 - 8,127 6,769 5.4

Energy Export 0 0 0.0

TOTAL PROCESS ENERGY 19,134 - 28,736 24 19.2

d 23,080 23,080 18.5
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 42,214 - 51,816 47,015 37.6

Feedstock Process Energye 15,928 15,928 12.7

TOTAL ENERGY EMBODIED IN 58,142 - 67,744 62,943 50.3

NYLON 6,6 MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of adipic acid and HMDA (Perry 1984). Stoichiometric ratios: 0.63 lbs
adipic acid and 0.53 lbs HMDA for every lb of Nylon 6,6 (ANL 1980, Brown 1996).
e Energy used to manufacture adipic acid and HMDA, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies (ANL 1980, Brown 1996).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (0.8 billion lbs) (CMA 1998). Assumes 2/3
of nylon market is Nylon 6,6.

135
 Table 4-15. Estimated Energy Use in Manufacture of Nylon 6 - 1997
Average Specific f Energy Chemical Industry Energy
Energy (Btu/lb) Use g (1012 Btu)

Electricitya 1,520 0.6

Energy for Steam/Process Heat f

Fuel Oil and LPGb 300 0.1

Natural Gas 7,690 3.1

Coal and Coke 999 0.4

Otherc 999 0.4

NET PROCESS ENERGY 11,507 4.6

Electricity Losses 3,156 1.3

Energy Export 0 0.0

TOTAL PROCESS ENERGY 14,663 5.9

d 22,000 8.8
Heat of Feedstock ()
)Hc)

TOTAL PRIMARY ENERGY 36,663 14.7

Feedstock Process Energye 16,821 6.7

TOTAL ENERGY EMBODIED IN 53,484 21.4

NYLON 6 MFG

a Does not includes losses incurred during the generation and transmission of electricity.
b LPG includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed.
d Feedstock energy based on heat of combustion of caprolactam (estimated). Stoichiometric ratios: 1.1 lbs caprolactam for
every lb of Nylon 6 (Brown 1996).
e Energy used to manufacture caprolactam, including all steps beginning with raw crude.
f Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for licensed technologies (Brown 1996).
g Calculated by multiplying average energy use (Btu/lb) by1997 production values (0.4 billion lbs) (CMA 1998). Assumes 1/3
of nylon market is Nylon 6.

136
4.4 Air Emissions emissions consisting of unreacted styrene,
which is flashed from the polymer in a vacuum
but becomes extremely dilute through air
Fugitive Emissions Are the Primary
leakage. The stream is exhausted through a
Source of Air Contaminants in the BTX
vacuum system and an oil demister to remove
Chain
the organic mist before being vented to the
atmosphere. The extruder quench vent is a large
The primary sources of emissions in the BTX
source of emissions, consisting primarily of
chain are fugitive and point air source emissions
styrene in water vapor. This stream is usually
from volatile compounds emitted from
vented through a forced draft hood and then
equipment and process operations. Fugitive
passed through a mist separator or electrostatic
emissions of volatile compounds arise from
precipitator before passing to the atmosphere.
leaks in valves, pumps, tanks, flanges, and
similar sources. While individual leaks may be
Emissions from polystyrene plants vary
minor, the combined fugitive emissions from
considerably, depending on the type of vacuum
various sources can be substantial in amount.
system employed. Plants using steam ejectors
typically produce VOC emissions at an elevated
Benzene is considered a human carcinogen and
rate. Condenser operating parameters also have
is highly toxic and flammable. It is among the
a substantial impact on emissions, and these
top twenty toxic chemicals released every year,
vary greatly between plants. Most polystyrene
primarily from point air and fugitive emission
plants do not use VOC control devices other
sources. Toluene, xylene, cumene, styrene,
than condensers (EPA 1991b).
and phthalic anhydride are also toxic
chemicals that are released by fugitive and point
Combustion of fuels in boilers to produce steam
air sources during their manufacture and use in
and in process heaters or furnaces also produce
chemical processing. Styrene is also a
criteria air pollutants that are regulated under
suspected human carcinogen. Emissions of
the Clean Air Act. The burning of cleaner fuels
these compounds are reported annually in the
such as natural gas in these heating units creates
Toxic Release Inventory (TRI) (e.g., EPA
relatively low emissions of SOx, NOx, CO,
1993a, 1994b, 1998).
particulates, and volatile hydrocarbons.
Present-day emission factors for process heaters
Air releases of benzene from the entire organic
and boilers are discussed in Section 7,
chemical sector (SIC 286) that were reported to
Supporting Processes.
the TRI were 1.4 million pounds in 1995. Air
releases of toluene (a non-carcinogenic toxin)
from the organic chemicals sector that were 4.5 Effluents
reported to the TRI were about 2.2 million
pounds in 1995, although many of these releases Liquid Wastes Are Primarily Process
originated from the use of toluene as a solvent, Wash Water
rather than in chemical reactions. Releases of p-
xylene were also significant in 1995–about 1.5 Effluents emitted during the production of BTX
million pounds (EPA 1998). and its derivatives consist primarily of wash
waters from crystallization operations, process
Volatile emissions from the production of water from distillation towers, and cooling
polystyrene include styrene, ethylbenzene, water. Much of this process water is recycled
additives, and small amounts of other volatile for reuse. Wash waters containing solvents are
organic compounds. Table 4-16 lists estimated usually sent to solvent recovery systems to
emission factors for volatile compounds emitted recover water and control volatile solvent
during polystrene production by the continuous emissions. Wastewater containing hazardous or
bulk polymerization process (EPA 1991b). The toxic components is often subjected to stripping
major vent is the devolatilizer condenser, with to separate contaminants so water can be reused.

137
Allowable limits for toxic or hazardous document, where there is a discussion of general
compounds contained in these wastewaters are water treatment processes. Specific limitations
given by the U.S. Environmental Protection are given for benzene, ethylbenzene, and
Agency in 40 CFR, Chapter 1, Part 414, which toluene, and for their chlorinated derivatives, as
was promulgated in 1974 and revised several shown in Table 4-17.
times since. The chemicals in the BTX chain
are covered under Subparts C, D, F, and G in
Part 414 of the CFR. The limitations for BTX
chemicals are summarized together in Section 7,
Supporting Processes, of this present

Table 4-16. Air Emission Factors for Continuous Processing of

Polystyrene (Grams VOC/kilogram product)
Nonmethane Volatile Organics
Type of Fiber
Uncontrolled Controlled
Styrene monomer storage 0.08

Additives
General Purpose 0.002
High Impact 0.001

Ethylbenzene Storage 0.001

Dissolvers 0.008
0.04d
Devolatilizer Condenser Vent 0.05a
2.96b

Styrene Recovery Unit 0.05a

Condenser Vent 0.13b

Extruder Quench Vent 0.01a

0.13b,c

Pellet Storage negligible

General Purpose Storage 0.008

High Impact Storage 0.007

TOTAL PLANT 0.21a

3.34b

Source: EPA 1991b.

a For plants using vacuum pumps.

b For plants using steam injector jets.
c Plant uses an organic scrubber to reduce emissions, and nonsoluble organics are burned as fuel. This factor
may vary significantly depending on overall process.
d Condenser is used downstream of primary process condensers; includes emissions from dissolvers; plant uses
vacuum pumps.

138
 Table 4-17. Effluent Pretreatment Standards
Maximum for any 1 Maximum for Monthly
Effluent day Average
(micrograms/liter) (micrograms/liter)
Benzene 134 57

Ethylbenzene 380 142

Toluene 74 28

Chlorobenzene 380 142

1,2,4-Trichlorobenzene 794 196

Hexachlorobenzene 794 196

1,2-Dichlorobenzene 794 196

1,3-Dichlorobenzene 380 142

1,4-Dichlorobenzene 380 142

Nitrobenzene 6,402 2,237

2-Nitrophenol 231 65

4-Nitrophenol 576 162

Source: 40 CFR Chapter 1, Part 414, Organic Chemicals, Plastics and Synthetic Fibers

4.6 Wastes, Residuals, and
Byproducts
Hazardous Wastes Are Associated with
Production of BTX and Derivatives
The EPA classifies a number of the wastes
associated with the production of BTX and its
derivatives as hazardous under Title 40 Code of
Federal Regulations (CFR), Part 261, Section 32
(see Table 4-18). Some of these wastes are
produced during the manufacture of these
chemicals, and some are produced during their
use as solvents. Toluene, benzene, xylene,
phthalic anhydride, phenol, and acetone (as well
as chlorinated derivatives of these compounds)
are all hazardous constituents and any waste
stream containing these compounds must be
treated as a hazardous waste.
processes discussed in this section, but are
products of the BTX chain. These include
dinitrotoluene, toluenediamine, toluene
diisocyanate, and others. While these are
relatively minor products, they contribute
significantly to the waste management burden
associated with BTX derivatives. Further, the
chlorinated BTX derivatives (chlorinated
benzenes, phenols) are not included in this table.
There are many options available for the
management of hazardous wastes, ranging from
incineration, which destroys the hazardous
components, to various treatment technologies
that convert hazardous to non-hazardous
components. For information on specific
treatment processes for hazardous wastes, refer
to one of the many sources published on this
topic.

Some of the hazardous wastes listed in Table 4-

18 are not the products of specific chemical

139
 Table 4-18. Hazardous Wastes from Production and Use of
BTX and Derivatives
Waste Hazardous
Number Description Constituents
F003 Spent non-halogenated solvents, including xylene and acetone. Includes Xylene, acetone
all spent solvent mixtures/blends containing, before use, one or more of
the aforementioned spent non-halogenated solvents; a spent solvent
mixture/blend containing a total of 10 percent or more (by volume) of one
of the solvents; and still bottoms from the recovery of these spent
solvents and solvent mixtures.

F005 Spent non-halogenated solvents including toluene and benzene. Toluene, benzene
Includes all solvent mixtures/blends containing a total of 10 percent or
more (by volume) of one or more of the aforementioned spent solvents;
and still bottoms from the recovery of these spent solvents and solvent
mixtures.

K022 Distillation bottom tars from the production of phenol/acetone from cumene Phenol, tars (polycyclic
aromatic hydrocarbons)

K023 Distillation light ends from the production of phthalic anhydride from Phthalic anhydride,
naphthalene maleic anhydride

K024 Distillation bottoms from the production of phthalic anhydride from Phthalic anhydride, 1-4,
naphthalene naphthoquinone

K025 Distillation bottoms from the production of nitrobenzene from benzene Meta-dinitrobenzene,
2,4-dinitrotoluene

K093 Distillation light ends from the production of phthalic anhydride Phthalic anhydride,
from o-xylene maleic anhydride

K094 Distillation bottoms from the production of phthalic anhydride from o-xylene Phthalic anhydride

K111 Product washwaters from the production of dinitro-toluene via nitration of 2,4-dinitrotoluene
toluene

K112 Reaction by-product water from the drying column in the production of 2,4-Toluenediamine, o-
toluenediamine via hydrogenation of dinitro-toluene toluidine, p-toluidine,
aniline

K113 Condensed liquid light ends from the purification of toluenediamine in the 2,4-Toluenediamine, o-
production of toluenediamine via hydrogenation of dinitrotoluene toluidine, p-toluidine,
aniline

K114 Vicinals from the purification of toluenediamine in the production of 2,4-Toluenediamine, o-

toluenediamine via hydrogenation of dinitrotoluene toluidine, p-toluidine,
aniline

K115 Heavy ends from the purification of toluenediamine in the production of 2,4-Toluenediamine
toluenediamine via hydrogenation of dinitrotoluene

K116 Organic condensate from the solvent recovery column in the production Carbon tetrachloride,
of toluene diisocyanate via phosgenation of toluenediamine tetrachloroethylene,
chloroform, phosgene

Source: BNA 1995.

140